EP0308803A2 - A mixture containing stabilised aromatic polyether ketones, and its use in the preparation of moulded products - Google Patents

A mixture containing stabilised aromatic polyether ketones, and its use in the preparation of moulded products Download PDF

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Publication number
EP0308803A2
EP0308803A2 EP88115059A EP88115059A EP0308803A2 EP 0308803 A2 EP0308803 A2 EP 0308803A2 EP 88115059 A EP88115059 A EP 88115059A EP 88115059 A EP88115059 A EP 88115059A EP 0308803 A2 EP0308803 A2 EP 0308803A2
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Prior art keywords
mixture according
radicals
compounds
polyether
weight
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German (de)
French (fr)
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EP0308803A3 (en
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Eckart Dr. Reske
Arnold Dr. Schneller
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the invention relates to a thermoplastic mixture consisting of at least one aromatic polyether ketone, at least one phosphorus compound and optionally at least one further polymer from the group of polycarbonates, polyesters, acrylonitrile / butadiene / styrene copolymers, polyether imides, polyether sulfones, polyether ketones and conventional additives and the use of Mixture for the production of molded parts.
  • the class of aromatic polyether ketones are known from the literature (US Pat. No. 4,108,837, US Pat. No. 3,332,909). They are high-melting and high-temperature stable thermoplastic polymers that are used in functional parts subject to high thermal stress. The processing of the polyether ketones takes place at temperatures above the melting temperature, generally at 350-450 ° C. Due to the high temperatures, a constant viscosity is necessary for uniform processing.
  • the object of the present invention is, on the one hand, to find stabilizers for compositions containing aromatic polyether ketones which suppress side reactions which lead to changes in viscosity at elevated temperatures during processing and, on the other hand, to optimize the polyether ketone / stabilizer system.
  • the polyether ketones used in the mixtures according to the invention are e.g. by polycondensation from aromatic dihydroxy compounds and - activated by electronegative groups - dihalo compounds (GB-PS 1 559 709, EP-B-0 000 361, EP-AO 152 161, DE-PS 2 220 079 and EP-A-0 195 448 ).
  • a preferred polyether ketone has the repeating unit in formula (I) in which A, B and B 'is phenylene, preferably p-phenylene, a and b is 1 and Y is -0-.
  • diphenols and / or further dihalogen compounds can optionally also be added in the polycondensation. In this way it is possible to set the desired content of recurring units of the formula (I) in the polyether ketones.
  • L and N are identical or different divalent aromatic radicals with 6-12 carbon atoms such as naphthylene, diphenylene, preferably phenylene, in particular m- and p-phenylene, but which can also be substituted with C1-C4-alkyl.
  • M is a simple bond or a divalent radical and means O, S, SO, SO2, CO, CH2 or C (CT3) 2, where T is hydrogen or halogen, preferably fluorine.
  • diphenols examples include hydroquinone, 2-phenylhydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxydiphenyl, 4,4'-dihydroxy-diphenylsulfone, 4,4'- Dihydroxy-benzophenone, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and bis (4-hydroxyphenyl) ether.
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • 4,4'-dihydroxydiphenyl 4,4'-dihydroxy-diphenylsulfone
  • 4,4'- Dihydroxy-benzophenone 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and bis (4-hydroxyphenyl) ether.
  • dihalogen compounds to be used are compounds of the general formula X1-D- (ZE) c -KG-X2 (IV)
  • X1 and X2 are different or preferably the same and represent halogen, preferably chlorine and fluorine.
  • D, E and G are independently divalent aromatic radicals with 6-12 carbon atoms such as phenylene, naphthylene, diphenylene, preferably phenylene, but which can also be substituted with C1-C4-alkyl.
  • D and G are always o- or p-linked, E can also be m-linked.
  • Z and K are -CO- or -SO2 and c is 1 or 2.
  • Preferred dihalogen compounds are, for example, 1- (4-fluorobenzoyl) -4- (2-fluorobenzoyl) benzene, 1,4- (bis- (4-fluorobenzoyl) benzene, 1- (4-chlorobenzoyl) -4- (2- Chlorobenzoyl) benzene, 1,4-bis (4-chlorobenzoyl) benzene.
  • the molar ratio of diphenols to the dihalogen compounds is generally 0.95 to 1.05: 1.05 to 0.95.
  • monophenols such as phenol (C6H5OH), p-phenylphenol and monohalogen compounds such as 4-fluorobenzophenone, 4-chloro or 4-fluorodiphenyl sulfone can be used in the polycondensation.
  • the polyether ketones used in the mixtures according to the invention have molecular weights (number average) from 5000 to 200000, preferably from 10000 to 100000.
  • polyether ketones of the formula (I) Another possibility for the preparation of polyether ketones of the formula (I) is the Friedel-Crafts reaction of diacyl halides with aromatic compounds with at least two hydrogen atoms in the presence of a catalyst.
  • DE-OS 16 45 153, US-PS 3,953,400 and US-PS 3,956,240 Another possibility for the preparation of polyether ketones of the formula (I) is the Friedel-Crafts reaction of diacyl halides with aromatic compounds with at least two hydrogen atoms in the presence of a catalyst.
  • Typical starting materials for the preparation of the polyether ketones by means of Friedel-Crafts acylation are terephthaloyl chloride or phosgene and diphenyl ether, optionally diphenoxybiphenyl, diphenoxybenzene or p-phenoxy-benzoyl chloride.
  • Polyether ketones produced by this process can also be modified with appropriate compounds in order to achieve the desired proportion of repeating units of the formula (I).
  • the polyether ketones generally consist of at least 70, preferably 80 to 100 and in particular 90 to 100% by weight of repeating units of the formula (I) and 0 to 30% by weight of further polymer units, the total always being 100% by weight. -% is.
  • R 1, R 2, R 3 are identical or different monovalent radicals having 1-50, preferably 2-18, carbon atoms. They can also contain heteroatoms, especially oxygen, phosphorus and nitrogen. Ionically bonded groups or atoms such as alkaline earth metals (in particular Ca) can also be part of these groups.
  • the radicals are preferably substituted or unsubstituted aromatic radicals such as phenyl, 2,4-di-tert-butyl-phenyl or 4-hydroxy-3,5-di-tert-butyl-benzyl radicals or radicals of the formulas
  • radicals can have the formula -OR.
  • R are e.g. Alkyl radicals such as the ethyl group or substituted or unsubstituted aromatic radicals e.g. Phenyl, 2,4-di-tert-butyl-phenyl or nonyl-phenyl residues.
  • Phosphorus compounds which are used alone or as a mixture in the mixtures according to the invention are, for example, triphenyl phosphate and phenylphosphates substituted with C1-C4-alkyl groups, such as tricresylphosphate, triphenylphosphite, substituted triphenylphosphites such as Tri- (nonylphenyl) phosphite, tri- (2,4-di-tert.butyl-phenyl) phosphite and compounds of the formulas
  • At least 2, in particular 2 to 5, phosphorus compounds are used in a mixture.
  • the sum of the phosphorus compounds used according to the invention is generally 0.01-5, preferably 0.05-2, particularly preferably 0.1-1% by weight, based on component (a).
  • the phosphorus compounds are mixed into the polyether ketones, and the mixtures are homogenized using suitable equipment such as kneaders, extruders or rollers above the melting temperatures of the products, generally at about 370-450 ° C.
  • suitable equipment such as kneaders, extruders or rollers above the melting temperatures of the products, generally at about 370-450 ° C.
  • the mixtures according to the invention can comprise further polymers c) from the group of polycarbonates, polyesters, acrylonitrile / butadiene / styrene copolymers, Contain polyimides, polyesterimides and polyether sulfones.
  • polycarbonates polyesters
  • acrylonitrile / butadiene / styrene copolymers Contain polyimides, polyesterimides and polyether sulfones.
  • polyether ketones are known in the literature (US 3,365,517; US 3,636,140; EP 211 604).
  • the aromatic polyether ketones and the additionally admixed polymers can be present in the mixtures according to the invention in any weight ratio.
  • Preferred mixing ratios are 10: 1 to 1: 5 parts by weight of polyether ketone: further polymer.
  • additives d) such as lubricants, flame retardants, non-stick agents, antistatic agents, plasticizers, fillers, pigments and reinforcing fibers (glass fibers, carbon fibers) can be incorporated into the polyether ketones in conventional amounts.
  • the mixtures according to the invention have improved stability at high temperatures. They can be processed into molded parts such as pipes, cable sheathing, circuit boards and various technical functional parts using the usual thermoplastic processing methods.
  • % is always% by weight.
  • the melt index is measured in accordance with DIN 53 735 at 400 ° C. under a load of 5 kp, the initial value being determined directly after 5 minutes after the sample has been introduced into the melt and the 30 min value 30 minutes after the introduction of the sample. Stability is given as a hundred times the ratio of the 30 min value to the 5 min value and is regarded as a measure of the change in the melt viscosity of the product under the action of the high temperature. If the melt viscosity does not change, the stability 100 results. 1. 7.708 kg of hydroquinone, 15.3 kg of sodium hydrogen carbonate and 70 kg of diphenyl sulfone were placed in a stirred kettle. The air was displaced by nitrogen and the mixture was heated to 140 ° C.
  • the mixture was then stirred at 140-150 ° C and heated to 210 ° C after the evolution of gas had ceased. 22.45 kg of 1,4-bis (4-fluorobenzoyl) benzene (BFB) was added. The temperature was raised to 310 ° C. within one hour. After a further 20 minutes, the reaction mixture was cooled, comminuted and washed alternately with water and sulfuric acid and with acetone to remove salts and diphenyl sulfone. The polymer powder was dried in a drying cabinet at 120 ° C./100 mbar.
  • BFB 1,4-bis (4-fluorobenzoyl) benzene
  • the polymer powder obtained was mixed with phosphorus compounds of the formula (II) with the addition of 0.1% each of polytetrafluoroethylene (PTFE) as a lubricant and extruded at 400.degree.
  • Comparative example 1 contained no phosphorus compound but only lubricant.
  • Table 1 also shows the melt index MFI and the stability of the mixtures.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract

Thermoplastic mixtures comprising at least one aromatic polyether ketone, at least one phosphorus compound and optionally at least one further polymer from the group comprising the polycarbonates, polyesters, acrylonitrile-butadiene-styrene copolymers, polyether- imides, polyether sulphones, polyether ketones and conventional additives are used to produce moulded products (mouldings).

Description

Die Erfindung betrifft eine thermoplastische Mischung bestehend aus mindestens einem aromatischen Polyetherketon, mindestens einer Phosphorverbindung und gegebenenfalls mindestens einem weiteren Polymerisat aus der Gruppe der Polycarbonate, Polyester, Acrylnitril/Butadien/Styrol-­Copolymerisate, Polyetherimide, Polyethersulfone, Polyetherketone und üblichen Zusatzstoffen sowie die Verwendung der Mischung zur Herstellung von Formteilen.The invention relates to a thermoplastic mixture consisting of at least one aromatic polyether ketone, at least one phosphorus compound and optionally at least one further polymer from the group of polycarbonates, polyesters, acrylonitrile / butadiene / styrene copolymers, polyether imides, polyether sulfones, polyether ketones and conventional additives and the use of Mixture for the production of molded parts.

Die Klasse der aromatischen Polyetherketone sind aus der Literatur bekannt (US-PS 4,108,837, US-PS 3,332,909). Sie stellen hochschmelzende und hochtemperaturstabile thermoplastische Polymere dar, die in thermisch stark beanspruchten Funktionsteilen eingesetzt werden. Die Verarbeitung der Polyetherketone erfolgt bei Temperaturen oberhalb der Schmelztemperatur, im allgemeinen bei 350 - 450 °C. Aufgrund der hohen Temperaturen ist eine Konstanz der Viskosität für eine gleichmäßige Verarbeitung notwendig.The class of aromatic polyether ketones are known from the literature (US Pat. No. 4,108,837, US Pat. No. 3,332,909). They are high-melting and high-temperature stable thermoplastic polymers that are used in functional parts subject to high thermal stress. The processing of the polyether ketones takes place at temperatures above the melting temperature, generally at 350-450 ° C. Due to the high temperatures, a constant viscosity is necessary for uniform processing.

Es ist bekannt, zur Stabilisierung von Polyetherketonen mit wiederkehrenden Einheiten der allgemeinen Formel -Ar-CO-­Phosphorverbindungen einzusetzen, wobei Ar ein divalentes aromatisches Radikal darstellt, das zumindest teilweise über Ethergruppierungen verknüpft ist (GB 1 446 962). Die angegebenen Beispiele zeigen jedoch, daß die Viskosität innerhalb einer Stunde stark schwankt, was vor allem bei der Spritzgußverarbeitung zu Problemen führt. Wünschenwert wäre eine Konstanz der Viskosität während der Verarbeitungszeit, so daß Maschinenparameter nicht geändert werden müssen.It is known to use -Ar-CO-phosphorus compounds for the stabilization of polyether ketones with recurring units of the general formula, where Ar is a divalent aromatic radical which is at least partially linked via ether groups (GB 1 446 962). However, the examples given show that the viscosity fluctuates greatly within one hour, which leads to problems, especially in injection molding processing. It would be desirable to have a constant viscosity during processing, so that machine parameters do not have to be changed.

Aufgabe der vorliegenden Erfindung ist es, zum einen Stabilisatoren für aromatische Polyetherketone enthaltende Massen zu finden, die Nebenreaktionen unterdrücken, welche zu Viskositätsveränderungen bei erhöhten Temperaturen während der Verarbeitung führen und zum anderen das System Polyetherketon/Stabilisator zu optimieren.The object of the present invention is, on the one hand, to find stabilizers for compositions containing aromatic polyether ketones which suppress side reactions which lead to changes in viscosity at elevated temperatures during processing and, on the other hand, to optimize the polyether ketone / stabilizer system.

Die geschilderten Nachteile lassen sich fast gänzlich ausschalten durch eine thermoplastische Mischung bestehend aus

  • (a) mindestens einem aromatischen Polyetherketon, das zu mindestens 70 Gew.-% die wiederkehrende Einheit
    Figure imgb0001
     und 0 bis 30 Gew.-% weitere Polymereinheiten, wobei die Summe stets 100 Gew.-% ist, enthält, wobei A, B und B′ gleiche oder verschiedene zweiwertige aromatische Reste mit 6 bis 12 C-Atomen darstellen, Y ein zweiwertiger Rest aus der Gruppe -O-, -S-, -SO-, -SO₂-, -CO, CH₂-, -C(CH₃)₂ ist, und a und b unabhängig voneinander 0 oder 1 sind,
  • (b) mindestens einer Phosphorverbindung der allgemeinen Formel
    Figure imgb0002
     wobei R¹, R² und R³ gleiche oder verschiedene einwertige Reste mit 1 bis 50 C-Atomen, oder solche Reste sind, die zusätzlich Heteroatome oder ionisch gebundene Gruppen oder Atome enthalten, X Schwefel oder Sauerstoff und n die Zahl 0 oder 1 bedeuten,
  • (c) gegebenenfalls mindestens einem weiteren Polymerisat aus der Gruppe der Polycarbonate, Polyester, Acylnitril/­Butadien/Styrol-Copolymerisate, Polyetherimide, Polyethersulfone, Polyetherketone und
  • (d) gegebenenfalls üblichen Zusatzstoffen.
The disadvantages described can be almost completely eliminated by a thermoplastic mixture consisting of
  • (a) at least one aromatic polyether ketone, which contains at least 70% by weight of the repeating unit
    Figure imgb0001
     and 0 to 30% by weight of further polymer units, the total always being 100% by weight, where A, B and B ′ represent identical or different divalent aromatic radicals having 6 to 12 carbon atoms, Y is a divalent radical from the group -O-, -S-, -SO-, -SO₂-, -CO, CH₂-, -C (CH₃) ₂, and a and b are independently 0 or 1,
  • (b) at least one phosphorus compound of the general formula
    Figure imgb0002
     where R¹, R² and R³ are identical or different monovalent radicals having 1 to 50 carbon atoms, or those radicals which additionally contain heteroatoms or ionically bonded groups or atoms, X is sulfur or oxygen and n is the number 0 or 1,
  • (c) optionally at least one further polymer from the group of polycarbonates, polyesters, acylnitrile / butadiene / styrene copolymers, polyetherimides, polyether sulfones, polyether ketones and
  • (d) optionally conventional additives.

Durch diese Maßnahme wird bewirkt, daß sich die normalerweise auftretende Veränderung der Schmelzviskosität der Polymeren bei hoher Temperatur so stark vermindert, daß eine Verarbeitung der Polymeren mit Hilfe der üblichen Methoden auch unter ungünstigen Bedingungen problemlos möglich wird. Hierbei hat sich herausgestellt, daß sich bei einer Mischung von Phosphorverbindungen ein synergistischer Effekt hinsichtlich der Wirksamkeit ergibt.This measure has the effect that the change in the melt viscosity of the polymers which normally occurs at high temperature is reduced to such an extent that processing of the polymers with the aid of the customary methods is possible without problems even under unfavorable conditions. It has been found that a mixture of phosphorus compounds results in a synergistic effect in terms of effectiveness.

Die in den erfindungsgemäßen Mischungen eingesetzten Polyetherketone werden in bekannter Weise z.B. durch Polykondensation aus aromatischen Dihydroxyverbindungen und - durch elektronegative Gruppen aktivierte - Dihalogenverbindungen hergestellt (GB-PS 1 559 709, EP-B-0 000 361, EP-A-O 152 161, DE-PS 2 220 079 und EP-A-0 195 448). Ein bevorzugtes Polyetherketon hat die wiederkehrende Einheit in Formel (I), in der A, B und B′ gleich Phenylen, vorzugsweise p-Phenylen, a und b gleich 1 und Y gleich -0- ist.The polyether ketones used in the mixtures according to the invention are e.g. by polycondensation from aromatic dihydroxy compounds and - activated by electronegative groups - dihalo compounds (GB-PS 1 559 709, EP-B-0 000 361, EP-AO 152 161, DE-PS 2 220 079 and EP-A-0 195 448 ). A preferred polyether ketone has the repeating unit in formula (I) in which A, B and B 'is phenylene, preferably p-phenylene, a and b is 1 and Y is -0-.

Neben den Dihydroxyverbindungen und den Dihalogenverbindungen, die zur Herstellung der Polyetherketone verwendet werden, können gegebenenfalls auch zusätzlich Diphenole und/oder weitere Dihalogenverbindungen bei der Polykondensation zugesetzt werden. Auf diese Weise ist es möglich, den gewünschten Gehalt an wiederkehrenden Einheiten der Formel (I) bei den Polyetherketonen einzustellen.In addition to the dihydroxy compounds and the dihalogen compounds which are used for the preparation of the polyether ketones, diphenols and / or further dihalogen compounds can optionally also be added in the polycondensation. In this way it is possible to set the desired content of recurring units of the formula (I) in the polyether ketones.

Dies sind Diphenole der Formel

HO-L-(Md-N)e-OH      (III)

in der d und e gleich oder verschieden sein können und die Werte 0 oder 1 annehmen. L und N sind gleiche oder verschiedene zweiwertige aromatische Reste mit 6-12 C-Atomen wie Naphthylen, Diphenylen, vorzugsweise Phenylen, insbesondere m- und p-Phenylen, die aber auch mit C₁-C₄-Alkyl substituiert sein können. M ist eine einfache Bindung oder ein zweiwertiger Rest und bedeutet O, S, SO, SO₂, CO, CH₂ oder C(CT₃)₂, wobei T Wasserstoff oder Halogen, vorzugsweise Fluor ist.These are diphenols of the formula

HO-L- (M d -N) e -OH (III)

in which d and e can be the same or different and assume the values 0 or 1. L and N are identical or different divalent aromatic radicals with 6-12 carbon atoms such as naphthylene, diphenylene, preferably phenylene, in particular m- and p-phenylene, but which can also be substituted with C₁-C₄-alkyl. M is a simple bond or a divalent radical and means O, S, SO, SO₂, CO, CH₂ or C (CT₃) ₂, where T is hydrogen or halogen, preferably fluorine.

Beispiele für derartige Diphenole sind Hydrochinon, 2-Phenylhydrochinon, Resorcin, 2,2-Bis(4-­hydroxyphenyl)propan (Bisphenol A), 4,4′-Dihydroxydiphenyl, 4,4′-Dihydroxy-diphenylsulfon, 4,4′-Dihydroxy-benzophenon, 2,2-Bis-(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluorpropan und Bis-(4-hydroxyphenyl)ether.Examples of such diphenols are hydroquinone, 2-phenylhydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxydiphenyl, 4,4'-dihydroxy-diphenylsulfone, 4,4'- Dihydroxy-benzophenone, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and bis (4-hydroxyphenyl) ether.

Beispiele für einzusetzende Dihalogenverbindungen sind Verbindungen der allgemeinen Formel

X¹-D-(Z-E)c-K-G-X²      (IV)

X¹ und X² sind verschieden oder vorzugsweise gleich und stellen Halogen dar, vorzugsweise Chlor und Fluor. D, E und G sind unabhängig voneinander zweiwertige aromatische Reste mit 6-12 C-Atomen wie Phenylen, Naphthylen, Diphenylen, vorzugsweise Phenylen, die aber auch mit C₁-C₄-Alkyl substituiert sein können. D und G sind stets o- oder p-­verknüpft, E kann außerdem auch m-verknüpft sein. Z und K sind -CO- oder -SO₂ und c ist 1 oder 2.Examples of dihalogen compounds to be used are compounds of the general formula

X¹-D- (ZE) c -KG-X² (IV)

X¹ and X² are different or preferably the same and represent halogen, preferably chlorine and fluorine. D, E and G are independently divalent aromatic radicals with 6-12 carbon atoms such as phenylene, naphthylene, diphenylene, preferably phenylene, but which can also be substituted with C₁-C₄-alkyl. D and G are always o- or p-linked, E can also be m-linked. Z and K are -CO- or -SO₂ and c is 1 or 2.

Bevorzugte Dihalogenverbindungen sind beispielsweise 1-(4-Fluorbenzoyl)-4-(2-fluorbenzoyl)-benzol, 1,4-(bis-(4-­Fluorbenzoyl)-benzol, 1-(4-Chlorbenzoyl)-4-(2-Chlorbenzoyl)-­benzol, 1,4-Bis-(4-Chlorbenzoyl)-benzol.Preferred dihalogen compounds are, for example, 1- (4-fluorobenzoyl) -4- (2-fluorobenzoyl) benzene, 1,4- (bis- (4-fluorobenzoyl) benzene, 1- (4-chlorobenzoyl) -4- (2- Chlorobenzoyl) benzene, 1,4-bis (4-chlorobenzoyl) benzene.

Das Molverhältnis von Diphenolen zu den Dihalogenverbindungen beträgt im allgemeinen 0,95 bis 1,05 : 1,05 bis 0,95.The molar ratio of diphenols to the dihalogen compounds is generally 0.95 to 1.05: 1.05 to 0.95.

Zur Blockierung von Endgruppen können bei der Polykondensation Monophenole wie Phenol (C₆H₅OH), p-Phenylphenol sowie Monohalogenverbindungen wie 4-Fluorbenzophenon, 4-Chlor- oder 4-Fluordiphenylsulfon verwendet werden.To block end groups, monophenols such as phenol (C₆H₅OH), p-phenylphenol and monohalogen compounds such as 4-fluorobenzophenone, 4-chloro or 4-fluorodiphenyl sulfone can be used in the polycondensation.

Die in den erfindungsgemäßen Mischungen eingesetzten Polyetherketone weisen Molekulargewichte (Zahlenmittel) von 5000 to 200000, vorzugsweise von 10000 bis 100000 auf.The polyether ketones used in the mixtures according to the invention have molecular weights (number average) from 5000 to 200000, preferably from 10000 to 100000.

Eine weitere Möglichkeit zur Herstellung von Polyetherketonen der Formel (I) besteht in der Friedel-Crafts-Reaktion von Diacylhalogeniden mit aromatischen Verbindungen mit mindestens zwei Wasserstoffatomen in Gegenwart eines Katalysators. (DE-OS 16 45 153, US-PS 3,953,400 und US-PS 3,956,240)Another possibility for the preparation of polyether ketones of the formula (I) is the Friedel-Crafts reaction of diacyl halides with aromatic compounds with at least two hydrogen atoms in the presence of a catalyst. (DE-OS 16 45 153, US-PS 3,953,400 and US-PS 3,956,240)

Typische Ausgangsmaterialien für die Herstellung der Polyetherketone mittels Friedel-Crafts-Acylierung sind Terephthaloylchlorid oder Phosgen und Diphenylether, gegebenenfalls Diphenoxybiphenyl, Diphenoxybenzol oder p-Phenoxy-benzoylchlorid. Auch nach diesem Verfahren hergestellte Polyetherketone können mit entsprechenden Verbindungen modifiziert werden, um den gewünschten Anteil an wiederkehrenden Einheiten der Formel (I) zu erreichen.Typical starting materials for the preparation of the polyether ketones by means of Friedel-Crafts acylation are terephthaloyl chloride or phosgene and diphenyl ether, optionally diphenoxybiphenyl, diphenoxybenzene or p-phenoxy-benzoyl chloride. Polyether ketones produced by this process can also be modified with appropriate compounds in order to achieve the desired proportion of repeating units of the formula (I).

Die Polyetherketone bestehen im allgemeinen zu mindestens 70, vorzugsweise zu 80 bis 100 und insbesondere 90 bis 100 Gew.-% aus wiederkehrenden Einheiten der Formel (I) und 0 bis 30 Gew.-% an weiteren Polymereinheiten, wobei die Summe stets 100 Gew.-% ist.The polyether ketones generally consist of at least 70, preferably 80 to 100 and in particular 90 to 100% by weight of repeating units of the formula (I) and 0 to 30% by weight of further polymer units, the total always being 100% by weight. -% is.

In den Phosphorverbindungen b) der allgemeinen Formel (II) sind R¹, R², R³ gleiche oder verschiedene einwertige Reste mit 1-50, vorzugsweise 2-18 C-Atomen. Sie können auch Heteroatome enthalten, insbesondere Sauerstoff, Phosphor und Stickstoff. Auch ionisch gebundene Gruppen oder Atome wie Erdalkalimetalle (insbesondere Ca) können Bestandteil dieser Gruppen sein. Vorzugsweise sind die Reste substituierte oder unsubstituierte aromatische Reste wie Phenyl-, 2,4-Di-tert.butyl-phenyl- oder 4-Hydroxy-3,5-di-­tert.butyl-benzyl-reste oder Reste der Formeln

Figure imgb0003
In the phosphorus compounds b) of the general formula (II), R 1, R 2, R 3 are identical or different monovalent radicals having 1-50, preferably 2-18, carbon atoms. They can also contain heteroatoms, especially oxygen, phosphorus and nitrogen. Ionically bonded groups or atoms such as alkaline earth metals (in particular Ca) can also be part of these groups. The radicals are preferably substituted or unsubstituted aromatic radicals such as phenyl, 2,4-di-tert-butyl-phenyl or 4-hydroxy-3,5-di-tert-butyl-benzyl radicals or radicals of the formulas
Figure imgb0003

Ferner können die Reste die Formel -OR besitzen. R sind z.B. Alkylreste wie die Ethylgruppe oder substituierte oder unsubstituierte aromatische Reste z.B. Phenyl-, 2,4-Di-tert-butyl-phenyl- oder Nonyl-phenyl-reste.Furthermore, the radicals can have the formula -OR. R are e.g. Alkyl radicals such as the ethyl group or substituted or unsubstituted aromatic radicals e.g. Phenyl, 2,4-di-tert-butyl-phenyl or nonyl-phenyl residues.

Phosphorverbindungen, die allein oder als Gemisch in den erfindungsgemäßen Mischungen eingesetzt werden, sind beispielsweise Triphenylphosphat sowie mit C₁-C₄-Alkylgruppen substituierte Phenylphosphate wie Trikresylphosphat, Triphenylphosphit, substituierte Triphenylphosphite wie Tri-(nonylphenyl)-phosphit, Tri-(2,4-di-tert.butyl-phenyl)-­phosphit sowie Verbindungen der Formeln

Figure imgb0004
Phosphorus compounds which are used alone or as a mixture in the mixtures according to the invention are, for example, triphenyl phosphate and phenylphosphates substituted with C₁-C₄-alkyl groups, such as tricresylphosphate, triphenylphosphite, substituted triphenylphosphites such as Tri- (nonylphenyl) phosphite, tri- (2,4-di-tert.butyl-phenyl) phosphite and compounds of the formulas
Figure imgb0004

Vorzugsweise werden mindestens 2, insbesondere 2 bis 5 Phosphorverbindungen im Gemisch eingesetzt.Preferably at least 2, in particular 2 to 5, phosphorus compounds are used in a mixture.

Die Summe der erfindungsgemäß eingesetzten Phosphorverbindungen beträgt im allgemeinen 0,01-5, vorzugsweise 0,05-2, besonders bevorzugt 0,1-1 Gew.-%, bezogen auf die Komponente (a).The sum of the phosphorus compounds used according to the invention is generally 0.01-5, preferably 0.05-2, particularly preferably 0.1-1% by weight, based on component (a).

Die Phosphorverbindungen werden den Polyetherketonen zugemischt, und die Mischungen mit Hilfe geeigneter Geräte wie Knetern, Extrudern oder Walzen oberhalb der Schmelztemperaturen der Produkte, im allgemeinen bei etwa 370-450 °C homogenisiert. Es ist jedoch auch möglich, die Phosphorverbindungen mit Hilfe der genannten Geräte in bereits geschmolzene Polyetherketone einzuarbeiten. Anschließend läßt man die Schmelze erkalten und zerkleinert die Produkte, die dann gebrauchsfertig sind.The phosphorus compounds are mixed into the polyether ketones, and the mixtures are homogenized using suitable equipment such as kneaders, extruders or rollers above the melting temperatures of the products, generally at about 370-450 ° C. However, it is also possible to incorporate the phosphorus compounds into already melted polyether ketones using the devices mentioned. The melt is then allowed to cool and the products are crushed, which are then ready for use.

Gegebenenfalls können die erfindungsgemäßen Mischungen weitere Polymerisate c) aus der Gruppe der Polycarbonate, Polyester, Acrylnitril/Butadien/Styrol-Copolymeren, Polyimide, Polyesterimide und Polyethersulfone enthalten. Diese Polymerisate, auch Mischungen mit Polyetherketonen, sind in der Literatur bekannt, (US 3,365,517; US 3,636,140; EP 211 604).If appropriate, the mixtures according to the invention can comprise further polymers c) from the group of polycarbonates, polyesters, acrylonitrile / butadiene / styrene copolymers, Contain polyimides, polyesterimides and polyether sulfones. These polymers, also mixtures with polyether ketones, are known in the literature (US 3,365,517; US 3,636,140; EP 211 604).

Die aromatischen Polyetherketone und die zusätzlich zugemischten Polymerisate können in jedem Gewichtsverhältnis in den erfindungsgemäßen Mischungen zugegen sein. Bevorzugte Mischungsverhältnisse sind 10:1 bis 1:5 Gewichtsteile Polyetherketon : weiteres Polymerisat.The aromatic polyether ketones and the additionally admixed polymers can be present in the mixtures according to the invention in any weight ratio. Preferred mixing ratios are 10: 1 to 1: 5 parts by weight of polyether ketone: further polymer.

Bei dem Mischprozeß können gleichzeitig übliche Zusätze d) wie Schmiermittel, flammhemmende Mittel, Antihaftmittel, Antistatika, Weichmacher, Füllstoffe, Pigmente und verstärkende Fasern (Glas-, Kohlefasern) in üblichen Mengen in die Polyetherketone eingearbeitet werden.In the mixing process, conventional additives d) such as lubricants, flame retardants, non-stick agents, antistatic agents, plasticizers, fillers, pigments and reinforcing fibers (glass fibers, carbon fibers) can be incorporated into the polyether ketones in conventional amounts.

Die erfindungsgemäßen Mischungen weisen eine verbesserte Stabilität bei hohen Temperaturen auf. Sie können mit Hilfe der üblichen Thermoplast-Verarbeitungsmethoden in Formteile wie Rohre, Kabelummantelungen, Platinen und diverse technische Funktionsteile verarbeitet werden.The mixtures according to the invention have improved stability at high temperatures. They can be processed into molded parts such as pipes, cable sheathing, circuit boards and various technical functional parts using the usual thermoplastic processing methods.

In den Beispielen ist % stets Gew.-%.In the examples,% is always% by weight.

BeispieleExamples

Der Schmelzindex wird nach DIN 53 735 bei 400 °C unter einer Last von 5 kp gemessen, wobei der Anfangswert direkt nach 5 Minuten nach dem Einbringen der Probe in die Schmelze und der 30 min-Wert 30 Minuten nach dem Einbringen der Probe bestimmt wird. Als Stabilität wird das Hundertfache des Verhältnisses des 30 min-Wertes zum 5 min-Wert angegeben und als Maß für die Veränderung der Schmelzviskosität des Produkts unter Einwirkung der hohen Temperatur angesehen. Ändert sich die Schmelzviskosität nicht, so ergibt sich die Stabilität 100.
1. 7,708 kg Hydrochinon, 15,3 kg Natriumhydrogencarbonat und 70 kg Diphenylsulfon wurden in einen Rührkessel gegeben. Die Luft wurde durch Stickstoff verdrängt und die Mischung auf 140 °C erhitzt. Anschließend wurde bei 140-150°C gerührt und nach dem Nachlassen der Gasentwicklung auf 210 °C erhitzt. 22,45 kg 1,4-Bis-(4-fluorbenzoyl)-benzol (BFB) wurden zugefügt. Innerhalb einer Stunde wurde die Temperatur auf 310 °C erhöht. Nach weiteren 20 Minuten wurde die Reaktionsmischung abgekühlt, zerkleinert und zur Entfernung von Salzen und Diphenylsulfon wechselweise mit Wasser und Schwefelsäure und mit Aceton gewaschen. Das Polymerpulver wurde im Trockenschrank bei 120 °C/100 mbar getrocknet.
2-4, Vergleich 1) Das erhaltende Polymerpulver wurde erfindungsgemäß mit Phosphorverbindungen der Formel (II) unter Zugabe von jeweils 0,1 % Polytetrafluorethylen (PTFE) als Schmiermittel gemischt und bei 400 °C extrudiert. Vergleichsbeispiel 1 enthielt keine Phosphorverbindung sondern nur Schmiermittel.
Die folgende Tabelle 1 zeigt ferner den Schmelzindex MFI und die Stabilität der Mischungen an. Tabelle 1 Beispiel Zusatz MFI Stabilität 5 min 30 min [g/10 min] 2 0,1 % PTFE + 0,25 % Triphenylphosphit 26 6,5 25 3 0,1 % PTFE + 0,25 % Triphenylphosphat 21 6,9 33 4 0,1 % PTFE + 0,125 % Triphenylphosphit + 0,125 % Triphenylphosphat 24 19 79 Vergleich 1 0,1 % PTFE 20 3,4 17
5) 19,22 kg BFB, 8,26 kg Soda und 55,5 kg Diphenylsulfon wurden in einen Rührkessel gegeben. Nach Ersatz der Luft durch Stickstoff wurde unter Rühren auf 220 °C erhitzt. Im Laufe von 4 Std. wurden 6,873 kg Hydrochinon zugefügt, gleichzeitig wurde auf 310 °C erhitzt. Diese Temperatur ist nach 45 min erreicht worden und wurde konstant gehalten. Nach 4 Std. wurden noch 0,25 kg BFB zugefügt. Nach weiteren 15 min wurde die Reaktionsmischung abgekühlt und wie im Beispiel 1 aufgearbeitet.
6-8, Vergleich 2) Aus dem Polymerpulver des Beispiels 5 wurden, wie bei Beispiel 2 beschrieben, folgende Mischungen hergestellt.

Figure imgb0005
Die folgende Tabelle 2 zeigt die an diesen Mischungen gemessenen Werte: Tabelle 2 Beispiel-Nr. MFI Stabilität 5 min 30 min [g/10 min] 6 24 17,5 73 7 22 15 68 8 23 19,3 84 Vergleich 2 22 10,6 48
9), Vergleich 3) Das Polymere aus Beispiel 5 wurde versetzt mit 0,1 % PTFE, 0,1 % Triphenylphosphat und 0,1 % Tri-(2,4-di-tert.butyl-phenyl)-phosphit und in einer handelsüblichen Spritzgußmaschine verarbeitet. Als Maß für die Stabilität des Produktes wurde die Fließweglänge in Abhängigkeit der Verweilzeit gemessen. Als Vergleich 3 dient die Mischung ohne die Phosphorverbindungen. Die erhaltenen Werte sind in der Tabelle 3 angeführt. Tabelle 3 Fließlänge in cm in Abhängigkeit von der Verweilzeit (in min) 0 5 15 30 60 [min] Beispiel 9 23 23 23 22,5 22,5 [cm] Vergleich 3 (nicht stabilisiert) 18 16 13 11 10 [cm] Aus der Tabelle ist zu entnehmen, daß die von der Viskosität abhängige Fließlänge der erfindungsgemäßen Mischung über die Verweilzeit von 60 Minuten praktisch konstant ist ( minus 2 %), während die Fließlänge, in der sich eine Veränderung der Viskosität ausdrückt, einer nicht stabilisierten Probe in diesem Zeitraum um ca. 45 % abnimmt.The melt index is measured in accordance with DIN 53 735 at 400 ° C. under a load of 5 kp, the initial value being determined directly after 5 minutes after the sample has been introduced into the melt and the 30 min value 30 minutes after the introduction of the sample. Stability is given as a hundred times the ratio of the 30 min value to the 5 min value and is regarded as a measure of the change in the melt viscosity of the product under the action of the high temperature. If the melt viscosity does not change, the stability 100 results.
1. 7.708 kg of hydroquinone, 15.3 kg of sodium hydrogen carbonate and 70 kg of diphenyl sulfone were placed in a stirred kettle. The air was displaced by nitrogen and the mixture was heated to 140 ° C. The mixture was then stirred at 140-150 ° C and heated to 210 ° C after the evolution of gas had ceased. 22.45 kg of 1,4-bis (4-fluorobenzoyl) benzene (BFB) was added. The temperature was raised to 310 ° C. within one hour. After a further 20 minutes, the reaction mixture was cooled, comminuted and washed alternately with water and sulfuric acid and with acetone to remove salts and diphenyl sulfone. The polymer powder was dried in a drying cabinet at 120 ° C./100 mbar.
2-4, Comparison 1) According to the invention, the polymer powder obtained was mixed with phosphorus compounds of the formula (II) with the addition of 0.1% each of polytetrafluoroethylene (PTFE) as a lubricant and extruded at 400.degree. Comparative example 1 contained no phosphorus compound but only lubricant.
The following Table 1 also shows the melt index MFI and the stability of the mixtures. Table 1 example additive MFI stability 5 min 30 min [g / 10 min] 2nd 0.1% PTFE + 0.25% triphenyl phosphite 26 6.5 25th 3rd 0.1% PTFE + 0.25% triphenyl phosphate 21st 6.9 33 4th 0.1% PTFE + 0.125% triphenyl phosphite + 0.125% triphenyl phosphate 24th 19th 79 Comparison 1 0.1% PTFE 20th 3.4 17th
5) 19.22 kg of BFB, 8.26 kg of soda and 55.5 kg of diphenyl sulfone were placed in a stirred kettle. After replacing the air with nitrogen, the mixture was heated to 220 ° C. with stirring. 6.873 kg of hydroquinone were added over the course of 4 hours, and the mixture was heated to 310 ° C. at the same time. This temperature was reached after 45 minutes and was kept constant. After 4 hours, 0.25 kg of BFB were added. After a further 15 minutes, the reaction mixture was cooled and worked up as in Example 1.
6-8, comparison 2) The following mixtures were prepared from the polymer powder of Example 5 as described in Example 2.
Figure imgb0005
The following Table 2 shows the values measured on these mixtures: Example No. MFI stability 5 min 30 min [g / 10 min] 6 24th 17.5 73 7 22 15 68 8th 23 19.3 84 Comparison 2 22 10.6 48
9), comparison 3) The polymer from Example 5 was mixed with 0.1% PTFE, 0.1% triphenyl phosphate and 0.1% tri- (2,4-di-tert-butyl-phenyl) phosphite and in one commercial injection molding machine processed. The flow path length as a function of the residence time was measured as a measure of the stability of the product. The mixture without the phosphorus compounds serves as comparison 3. The values obtained are shown in Table 3. Flow length in cm depending on the dwell time (in min) 0 5 15 30th 60 [min] Example 9 23 23 23 22.5 22.5 [cm] Comparison 3 (not stabilized) 18th 16 13 11 10th [cm] From the table it can be seen that the flow length of the mixture according to the invention, which is dependent on the viscosity, is practically constant (minus 2%) over the residence time of 60 minutes, while the flow length, in which a change in the viscosity is expressed, of an unstabilized sample in this period decreases by approx. 45%.

Claims (15)

1. Thermoplastische Mischung bestehend aus (a) mindestens einem aromatischen Polyetherketon, das zu mindestens 70 Gew.-% die wiederkehrende Einheit
Figure imgb0006
 und 0 bis 30 Gew.-% weitere Polymereinheiten, wobei die Summe stets 100 Gew.-% ist, enthält, wobei A, B und B′ gleiche oder verschiedene zweiwertige aromatische Reste mit 6 bis 12 C-Atomen darstellen, Y ein zweiwertiger Rest aus der Gruppe -O-, -S-, -SO, -SO₂-, -CO, CH₂-, -C(CH₃)₂ ist, und a und b unabhängig voneinander 0 oder 1 sind, (b) mindestens einer Phosphorverbindung der allgemeinen Formel
Figure imgb0007
 wobei R¹, R² und R³ gleiche oder verschiedene einwertige Reste mit 1 bis 50 C-Atomen, oder solche Reste sind, die zusätzlich Heteroatome oder ionisch gebundene Gruppen oder Atome enthalten, X Schwefel oder Sauerstoff und n die Zahl 0 oder 1 bedeuten, (c) gegebenenfalls mindestens einem weiteren Polymerisat aus der Gruppe der Polycarbonate, Polyester, Acylnitril/­Butadien/Styrol-Copolymerisate, Polyetherimide, Polyethersulfone, Polyetherketone und (d) gegebenenfalls üblichen Zusatzstoffen. 1. Thermoplastic mixture consisting of (a) at least one aromatic polyether ketone, which contains at least 70% by weight of the repeating unit
Figure imgb0006
 and 0 to 30% by weight of further polymer units, the total always being 100% by weight, where A, B and B ′ represent identical or different divalent aromatic radicals having 6 to 12 carbon atoms, Y is a divalent radical from the group -O-, -S-, -SO, -SO₂-, -CO, CH₂-, -C (CH₃) ₂, and a and b are independently 0 or 1, (b) at least one phosphorus compound of the general formula
Figure imgb0007
 where R¹, R² and R³ are identical or different monovalent radicals having 1 to 50 carbon atoms, or those radicals which additionally contain heteroatoms or ionically bonded groups or atoms, X is sulfur or oxygen and n is the number 0 or 1, (c) optionally at least one further polymer from the group of polycarbonates, polyesters, acylnitrile / butadiene / styrene copolymers, polyetherimides, polyether sulfones, polyether ketones and (d) optionally conventional additives. 2. Mischung nach Anspruch 1, dadurch gekennzeichnet, daß die Polyetherketone zu 80 bis 100 Gew.-%, insbesondere zu 90 bis 100 Gew.-% die wiederkehrende Einheit (I) enthalten.2. Mixture according to claim 1, characterized in that the polyether ketones contain 80 to 100% by weight, in particular 90 to 100% by weight, of the repeating unit (I). 3. Mischung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß in dem Polyetherketon die wiederkehrende Einheit die Formel (I) hat, in der A, B und B′ gleich Phenylen, vorzugsweise p-Phenylen, a und b gleich 1 und Y gleich -0- ist3. Mixture according to claim 1 or 2, characterized in that in the polyether ketone the repeating unit has the formula (I) in which A, B and B 'are phenylene, preferably p-phenylene, a and b are 1 and Y is the same -0- is 4. Mischung nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die weiteren Polymereinheiten von Diphenolen der allgemeinen Formel

HO-L-(Md-N)e-OH      (III)

abgeleitet sind, in der d und e gleich oder verschieden sind und die Werte 0 oder 1 annehmen, L und N gleiche oder verschiedene zweiwertige aromatische Reste mit 6 - 12 C-Atomen sind, die gegebenenfalls mit C₁-C₄-Alkyl substituiert sind, M ist eine einfache Bindung oder ein zweiwertiger Rest aus der Gruppe O, S, SO, SO₂, CO, CH₂ oder C(CT₃)₂ ist, wobei T Wasserstoff oder Halogen, vorzugsweise Fluor ist, und/oder von Dihalogenverbindungen der allgemeinen Formel

X¹-D-(Z-E)c-K-G-X²      (IV)

abgeleitet sind, bei der X¹, X² gleich oder verschieden sind und Halogen, D, E und G gleich oder verschieden sind und zweiwertige aromatische Reste mit 6 - 12 C-Atomen, von denen D und G stets o- oder p-verknüpft sind, Z und K die -CO- oder -SO₂-Gruppe und c die Zahl 1 oder 2, jeweils unabhängig voneinander, bedeuten.4. Mixture according to one or more of claims 1 to 3, characterized in that the further polymer units of diphenols of the general formula

HO-L- (M d -N) e -OH (III)

are derived in which d and e are the same or different and assume the values 0 or 1, L and N are the same or different divalent aromatic radicals having 6 to 12 carbon atoms, which are optionally substituted by C₁-C₄-alkyl, M is a simple bond or a divalent radical from the group O, S, SO, SO₂, CO, CH₂ or C (CT₃) ₂, where T is hydrogen or halogen, preferably fluorine, and / or of dihalo compounds of the general formula

X¹-D- (ZE) c -KG-X² (IV)

are derived, in which X¹, X² are identical or different and halogen, D, E and G are identical or different and divalent aromatic radicals having 6 to 12 carbon atoms, of which D and G are always o- or p-linked, Z and K represent the -CO or -SO₂ group and c the number 1 or 2, each independently of the other. 5. Mischung nach Anspruch 4, dadurch gekennzeichnet, daß X¹, X² unabhängig voneinander Chlor oder Fluor sind.5. Mixture according to claim 4, characterized in that X¹, X² are independently chlorine or fluorine. 6. Mischung nach Anspruch 4 oder 5, dadurch gekennzeichnet, daß die Diphenole Hydrochinon, Resorcin, Bisphenol A, 4,4′-Dihydroxydiphenyl, 4,4′-Dihydroxy-diphenylsulfon oder 4,4′-Dihydroxybenzophenon und die Dihalogenverbindungen 4,4′-Difluorbenzophenon, 4,4′-Dichlordiphenylsulfon, 4,4′-Difluordiphenylsulfon, 1,4-Bis-(4-Fluorbenzoyl)-benzol oder 1-(4-Fluorbenzoyl)-4-(2-fluorbenzoyl)benzol sind.6. Mixture according to claim 4 or 5, characterized in that the diphenols hydroquinone, resorcinol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxy-diphenyl sulfone or 4,4'-dihydroxybenzophenone and the dihalogen compounds 4,4 '-Difluorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 1,4-bis (4-fluorobenzoyl) benzene or 1- (4-fluorobenzoyl) -4- (2-fluorobenzoyl) benzene. 7. Mischung nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß in Komponente b) X Sauerstoff ist.7. Mixture according to one or more of claims 1 to 6, characterized in that in component b) X is oxygen. 8. Mischung nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Reste R¹, R², R³ 2-18 C-Atome aufweisen.8. Mixture according to one or more of claims 1 to 7, characterized in that the radicals R¹, R², R³ have 2-18 C atoms. 9. Mischung nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß in Komponente b) ein Teil oder alle Reste R¹, R², R³ als Heteroatome Sauerstoff und/oder Phosphor enthalten.9. Mixture according to one or more of claims 1 to 8, characterized in that in component b) part or all of the radicals R¹, R², R³ contain oxygen and / or phosphorus as heteroatoms. 10. Mischung nach einem oder mehreren der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß mindestens zwei der Reste R¹, R², R³ jeder Phosphorverbindung substituierte oder unsubstituierte aromatische Reste sind und/oder die Struktur -OR aufweisen.10. Mixture according to one or more of claims 1 to 9, characterized in that at least two of the radicals R¹, R², R³ of each phosphorus compound are substituted or unsubstituted aromatic radicals and / or have the structure -OR. 11. Mischung nach Anspruch 10, dadurch gekennzeichnet, daß die Reste -OR Phenoxy-, 2,4-Di-tert.butyl-phenoxy-, Nonylphenoxy- oder Äthoxy-Reste sind.11. Mixture according to claim 10, characterized in that the radicals are -OR phenoxy, 2,4-di-tert.butyl-phenoxy, nonylphenoxy or ethoxy radicals. 12. Mischung nach einem oder mehreren der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß als Phosphorverbindung mindestens eine, vorzugsweise mindestens zwei Verbindungen aus der Gruppe bestehend aus Triphenylphosphat, Triphenylphosphit, Tri-(2,4-di-tert-butyl-phenyl)-phosphit oder Verbindungen der Formeln
Figure imgb0008
 eingesetzt wird (werden).12. Mixture according to one or more of claims 1 to 11, characterized in that at least as the phosphorus compound one, preferably at least two compounds from the group consisting of triphenyl phosphate, triphenyl phosphite, tri- (2,4-di-tert-butylphenyl) phosphite or compounds of the formulas
Figure imgb0008
 is (are) used. 13. Mischung nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Summe der Phosphorverbindungen b) 0,01-5, vorzugsweise 0,05-2 und insbesondere 0,1-1 Gew.-%, bezogen auf Komponente a), beträgt.13. Mixture according to one or more of claims 1 to 12, characterized in that the sum of the phosphorus compounds b) 0.01-5, preferably 0.05-2 and in particular 0.1-1 wt .-%, based on the component a), is. 14. Verwendung der Mischungen gemäß einem oder mehreren der Ansprüche 1 bis 13 zur Herstellung von Formteilen.14. Use of the mixtures according to one or more of claims 1 to 13 for the production of moldings. 15. Verwendung nach Anspruch 14 als Rohre, Kabelummantelungen, Platinen und technische Funktionsteile.15. Use according to claim 14 as pipes, cable sheathing, circuit boards and technical functional parts.
EP19880115059 1987-09-19 1988-09-15 A mixture containing stabilised aromatic polyether ketones, and its use in the preparation of moulded products Withdrawn EP0308803A3 (en)

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DE3731607 1987-09-19
DE19873731607 DE3731607A1 (en) 1987-09-19 1987-09-19 STABILIZED MIXTURE CONTAINING AROMATIC POLYETHERKETONE AND THE USE THEREOF FOR THE PRODUCTION OF MOLDED PARTS

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EP0308803A2 true EP0308803A2 (en) 1989-03-29
EP0308803A3 EP0308803A3 (en) 1991-04-03

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EP19880115059 Withdrawn EP0308803A3 (en) 1987-09-19 1988-09-15 A mixture containing stabilised aromatic polyether ketones, and its use in the preparation of moulded products

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EP (1) EP0308803A3 (en)
JP (1) JPH01104650A (en)
DE (1) DE3731607A1 (en)

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EP0466002A1 (en) * 1990-07-12 1992-01-15 BASF Aktiengesellschaft Stabilized polyarylenetherketone moulding compounds
WO2008119677A1 (en) * 2007-04-02 2008-10-09 Solvay Advanced Polymers, L.L.C. New flexible pipe
WO2017013368A1 (en) * 2015-07-22 2017-01-26 Arkema France Composition made from poly(arylene-ether-ketone) (paek) stable in a molten state

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DE3936997A1 (en) * 1989-11-07 1991-05-08 Hoechst Ag SEMIPERMEABLE MEMBRANE MADE OF POLYETHERKETONES
JP7332837B2 (en) * 2021-07-30 2023-08-23 ポリプラスチックス株式会社 WHOLE AROMATIC ETHER KETONE RESIN COMPOSITION AND METHOD FOR MANUFACTURING THE SAME, MOLDED PRODUCT, AND METHOD FOR IMPROVING RETENTION STABILITY OF MELT VISCOSITY OF THE SAME RESIN COMPOSITION

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EP0148633A2 (en) * 1983-12-22 1985-07-17 Amoco Corporation Process for the preparation of polyaryletherketones
EP0268112A2 (en) * 1986-11-20 1988-05-25 Asahi Kasei Kogyo Kabushiki Kaisha A novel aromatic polyether and a process for producing a polyether

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0466002A1 (en) * 1990-07-12 1992-01-15 BASF Aktiengesellschaft Stabilized polyarylenetherketone moulding compounds
US5145894A (en) * 1990-07-12 1992-09-08 Juergen Koch Stabilized polyaryl ether ketone molding compositions containing a phosphorus compound
WO2008119677A1 (en) * 2007-04-02 2008-10-09 Solvay Advanced Polymers, L.L.C. New flexible pipe
WO2017013368A1 (en) * 2015-07-22 2017-01-26 Arkema France Composition made from poly(arylene-ether-ketone) (paek) stable in a molten state
WO2017013369A1 (en) * 2015-07-22 2017-01-26 Arkema France Method for stabilising a composition made from poly(arylene-ether-ketone) (paek)
FR3039157A1 (en) * 2015-07-22 2017-01-27 Arkema France STABLE-MADE STABLE POLYARYLENE-ETHER-KETONE (PAEK) COMPOSITION AND METHOD OF STABILIZING SUCH A COMPOSITION
CN107849238A (en) * 2015-07-22 2018-03-27 阿科玛法国公司 Method for making the composition stability made of poly- (arylene ether ketone) (PAEK)
CN107849237A (en) * 2015-07-22 2018-03-27 阿科玛法国公司 The stable composition made of poly- (arylene ether ketone) (PAEK) in the molten state
KR20180031735A (en) * 2015-07-22 2018-03-28 아르끄마 프랑스 Method for stabilising a composition made from poly(arylene-ether-ketone) (paek)
KR20180031734A (en) * 2015-07-22 2018-03-28 아르끄마 프랑스 Composition made from poly(arylene-ether-ketone) (paek) stable in a molten state
US20180201759A1 (en) * 2015-07-22 2018-07-19 Arkema France Composition made from poly(arylene-ether-ketone) (paek) stable in a molten state
CN107849237B (en) * 2015-07-22 2020-07-10 阿科玛法国公司 Composition made of poly (arylene-ether-ketone) (PAEK) stable in the molten state
EP3778708A1 (en) * 2015-07-22 2021-02-17 Arkema France Melt stable polyaryl-ether-ketone (paek) based composition
US10988596B2 (en) 2015-07-22 2021-04-27 Arkema France Method for stabilising a composition made from poly(arylene-ether-ketone) (PAEK)
CN107849238B (en) * 2015-07-22 2021-05-07 阿科玛法国公司 Method for stabilizing compositions made from poly (arylene-ether-ketones) (PAEKs)
CN113088062A (en) * 2015-07-22 2021-07-09 阿科玛法国公司 Method for stabilizing compositions made from poly (arylene-ether-ketones) (PAEKs)

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Publication number Publication date
DE3731607A1 (en) 1989-03-30
EP0308803A3 (en) 1991-04-03
JPH01104650A (en) 1989-04-21

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